(1) Field of the Invention
This invention relates to electrochemical cells and more particularly to electrolytic diaphragm cells having an electrolyte permeable diaphragm and at least one self-draining electrode contacting said electrolyte permeable diaphragm.
(2) Description of the Prior Art
Packed bed chlor-alkali electrolytic cells and electrolytic cells for the production of alkaline hydrogen peroxide solutions are known from Oloman et al U.S. Pat. No. 3,969,201 and U.S. Pat. No. 4,118,305. Improvements in these cells have been disclosed by McIntyre et al in U.S. Pat. No. 4,406,758; U.S. Pat. No. 4,431,494; U.S. Pat. No. 4,445,986; U.S. Pat. No. 4,511,441; and U.S. Pat. No. 4,457,953. These packed bed electrolytic cells are particularly useful for the production of alkaline solutions of hydrogen peroxide.
Among known bleaching agents, hydrogen peroxide is at the present time being increasingly used, in particular for bleaching materials such as textiles or paper pulp. Hydrogen peroxide has the great advantage over other bleaching agents, in particular chlorine and its compounds, in that because of its mild action, it attacks the fibers of the material to be treated to a much lesser extent, while exerting a more durable action and giving a better finish.
Hydrogen peroxide is generally used in bleaching in the form of a stabilized alkaline solution of low peroxide concentration. The action of the hydrogen peroxide in bleaching consists essentially of destroying or decolorizing the natural dyes by oxidation, or by rendering them soluble. Even though the mechanism of these reactions has not been studied exclusively, it is generally assumed that the hydrogen peroxide ion HOO- is responsible for the bleaching.
Present-day bleaching solutions based on hydrogen peroxide have the great disadvantage with respect to other conventional bleaching solutions (in particular hypochlorite-based solutions) of being relatively costly. Their widespread use is very dependent on economic considerations, particularly when large quantities of low-value material such as paper pulp are to be treated. Present-day bleaching solutions are nearly always prepared by simple dissolving and dilution, starting from commercially available chemicals. Commercially available hydrogen peroxide is a particularly costly substance, as it is manufactured only in a small number of large industrial plants, and, therefore, it has to be highly concentrated for storage and transport purposes before being distributed. At the present time, there is a need to replace the highly concentrated, commercially available hydrogen peroxide by on site manufacturing methods which enable dilute solutions of hydrogen peroxide to be produced directly, in order to reduce bleaching costs. However, up to the present time no satisfactory method has appeared.
Hydrogen peroxide is used not only for bleaching purposes, but also in an increasing number of other processes, in particular in the pollution control field. However, treatment solutions used for this purpose are likewise almost always prepared from highly concentrated hydrogen peroxide with the same disadvantages as heretofore stated.
In Grangaard, U.S. Pat. No. 3,607,687; U.S. Pat. No. 3,462,351; U.S. Pat. No. 3,507,769; and U.S. Pat. No. 3,592,749 there are disclosed electrolytic cells for the production of hydrogen peroxide in which the peroxide is produced in the cathode compartment of the cell which contains a cathode depolarized utilizing an oxygen containing gas. The electrochemical cells of Oloman et al and McIntyre et al disclosed in the patents cited above, are improvements over the cells of Grangaard partly as the result of the use of the novel electrode material disclosed in U.S. Pat. No. 4,457,953 in which there is disclosed a method for the production of coated particles for use in a packed bed electrode electrochemical cell.
It has been found that a packed bed electrode for maximum productivity within an electrochemical cell must be supplied with anolyte through an electrolyte porous diaphragm at a substantially uniform rate of flow across the porous diaphragm without appreciable variation of the flow rate at a function of the head of the electrolyte. Prior art porous diaphragms for packed bed electrolytic cells have permitted a considerable variation in flow rate with the flow rate at the base of the cell (exposed to the full head of the electrolyte) being appreciably faster than the flow rate in the center of the cell or at the top of the cell, where a decreased head pressure is exerted on the diaphragm. This variation in flow rate has resulted in the inefficiency of the cell as the result of flooding or starvation of the packed bed cathode Where an attempt has been made to reduce the flow rate through the cell diaphragm so as to prevent flooding of the packed bed cathode, it has been found that too little electrolyte passes through the porous diaphragm into the cathode (starvation) where the diaphragm is exposed to a minimal head of electrolyte. A reduced amount of electrolyte passing through the porous diaphragm into the cathode cell also results in an increase in cell voltage. An excessive amount of electrolyte passing through the porous diaphragm causes flooding of the packed bed cathode and consequent reduction in the depolarizing effect of the oxygen containing gas fed to the side of the packed bed cathode opposite to that which is exposed to the electrolyte.